Fatty amide polymers



Patented Nov. 5,

McLeod, ltumford, R. L, assi Hoffman & Co. Incorporated,

ore to Arnold, rovidence, R. I.,

a corporation of Rhode Island No Drawing. Application April 5, 1944, Serial No. 529,688

18 Claims. 1

This application is a continuation in part of our copending application Serial #357,443, filed September 19, 1940.

This invention relates to new condensation products which are suitable as assistants for the modification of the properties of textile fibers.

Many materials have been used as textile assistants for altering the softness, the easy wetting or the repellency of textile fibers, or for increasing the stiffness or apparent weight, but each has been subject to some fault; thus; tallows, oils, and sulphonated oils or tallows have long been used in the finishing of textiles for softening effects, but these effects are not permanent and are lost the first time the goods are washed. These materials also suffer from rancidity or objectionable odor development in the goods. Fatty alcohols and fatty alkyd resins have also been used as textile softeners, but these also wash out. Fatty amides and the quarternary salts of these, as well as fatty quaternaries produced from pyridine or the betaines, and fatty i-midazoles, have been suggested as textile modifying agents and in particular as textile softeners. While these materials are mostly fairly expensive and dark in color, these substances have shown the advantage of being somewhat resistant to washing. The quaternary salts of fatty acid condensations with aliphatic polyamines have also been used, particularly as these have shown a maximum resistance to washing up to this time. However, each of these types of materials has left considerable to be desired as with regards to resistance to washing and as each of these materials has been unstable with respect to heat and oxidation, their use has been attended with the serious difiiculty of the cloth being yellowed either by reason of the initially dark color of the product, or by its decomposition due to the heat used in drying the fabric. Furthermore, goods which have been finished with these materials have frequently during a few months storage become seriously yellow due to the softener being sensitive to oxidation.

Many resinous materials have also been applied to textiles for various types of modification of their properties. Among these we find the alkyds, fatty alkyds, methacrylates, and vinyls which, due to their general water insolubility and sticky nature, cause considerable dimculty as they must be applied in the form of dispersions which are generally unstable. These materials leave much to be desired in their permanency on cloth due to alteration on ageing and poor resistance to washing particularly in the case of the alkyds. Urea-formaldehyde resins have also been widely applied but these frequently impart odors to the cloth or tender it and the special high temperatures necessary for its baking call for expensive equipment.

It is an object of this invention to provide a new class of textile assistants such as wetting, softening, lubricating, waterproofing, and stiffening agents having improved properties. It is a further object to produce textile assistants which are resistant to heat and to oxidation which permit the finishing and storage of the finished goods for long periods without any yellowing, odor development, or tendering.

As further objects of our invention, we describe condensation products which may :be easily applied from aqueous solutions or dispersions to give finishes on cloth of a maximum softness, which effects are completely permanent to washins and to dry cleaning.

A further object of our invention is to provide condensation products of resinous nature which give permanent bodying or stiflness effects coupled with desirable soft feel. These materials, because of high effectiveness, can be economically used to replace sulphonated tallows in textile finishing. I

A still further object of our invention is to describe new condensation products and resinous materials which may be applied permanently to textile materials from aqueous solution without any special heating or baking of the treated cloth.

The condensation products proposed by this invention are resinous or semi-resinous materials in which dialkylol substituted carbamido compounds carrying side chains conta w .sit polyamino acid amide radicals are linked together by reaction with polybasic acids.

These compounds are readily prepared by reacting the carbamyl derivatives such as urea, thiourea, guanidine salts, biuret, diguanidine, or guanyl urea with the acid amide condensation products secured from aliphatic polyamines carrying hydroxyl groups and acids or acid esters or acid chlorides and thereafter reacting the products thus secured with polycarboxylic acids.

As suitable acids for forming the polyamino acid amides with the polyamines, we prefer those containing six or more carbons and preferably saturated aliphatic acids such as lauric, stearic, palm oil acids, although we may use the lower molecular weight aliphatic acids including acetic and we.

may use the unsaturated or substituted fatty acids, such as ricinoleic, oleic, sebacic or chlorostearlc, or the cycloaliphatic, aromatic, or resin acids may also be used, such as naphthenic, phthalic, benzcic, creostinic, and abietic, or the resin acid secured from rosin and maleic anhydride. These acids may be condensed with any hydroxyl substituted polyamines such as hydroxyethyl ethylene diamine, hydroxylethyl diethylene triamine, diamino propanols, such as 1-3 diamino propanols, N-3 amino 2 propanol ethylene diamine, or the alkylol substituted polyamines which are readily secured from ethylene or propylene oxide by reaction with polyamines. The polyamino acid amide products thus secured are reacted with the carbamyl derivatives alread indicated and thereafter the free hydroxyl groups are then reacted with polybasic acids such as succinic, maleic,

'sebacic, phthalic, and adipic.

The condensation products of this invention are materials of high molecular weight in which units of the following general formula are linked together at the dotted line in large numbers:

In this formula R1 is a hydrocarbon residue resulting from the dicarboxylic acid which has been used.

R: and R4 represent simple alkylene groups of from two to three carbon atoms. These groups and the adjacent nitrogen originate from the amine used in the condensation and attached to the'nitrogens N1 and N2 is the remaining part of the fatty amino acid amide as a side chain. The fatty acid precondensed with the amine forms the terminal part of the side chain. The amino acid amide side chains residues are of the following type in which the radicals may depend for their nature on the amine and the acid reacted therewith.

In this formula just given for the side chains of the polyamino acid amide type, R1 corresponds preferably to a saturated aliphatic chain such as would result from the use of a saturated fatty acid or any of the other various types of acids already enumerated; thus, R1 may also represent other hydrocarbon radicals such as a cyclo alkyl, an unsaturated hydrocarbon, an aryl radical, or a residue from a terpene acid. In each case the corresponding acid, acid chloride, or ester may be used as a source to introduce this radical into our condensation products as will be shown later.

The letters f, e, and m represent small integers, j varying from 2 to 6, e from 0 to 3 and m from 2 to 3, and any of the hydrogens in the CH2 groups may be substituted by a simple alkyl or hydroxy group. It is evident from the two general formulas above that the alkylol polyamine employed in producing the product has the following general formula:

wherein e varies from 0 to 3, f from 2 to 6, and m from 2 to 3.

The condensation products of this invention are in some cases directly water soluble or water dispersible. In most cases the condensations are readily dissolved after treatment with acids, such as acetic, lactic, boric, oxalic, benzcic, salicylic, furoic, citric, tartaric, formic, phthalic, succinic, or alkyl naphthalene sulphonic acids or after reaction with an alkylating agent, such as, ethyl chloride, benzyl chloride, ethylene oxide, ethylene chlorohydrin, diethyl sulphate, or dimethyl sulphate. The salts or alkylated products of our substituted new condensates are indicated in the general formula given where B represents the acid hydrogen or alkyl groups and X the acid radical or halogene group, while for our primary condensations B and X disappear from the formula.

The condensation products of this invention are readily prepared by heating equimolal quantities of the acid and hydroxylated amine at temperatures from to 200 C. until the reaction is complete as shown by the loss of one molecule of water. The mix is then cooled back to 180 and one half moi or more of the urea or other carbamyl derivative added. Ammonia is rapidly liberated as the urea becomes substituted, the temperature being held between 170 and 200 C. After holding the product for a short period up to one-half hour during which time the ammonia is driven off, preferably one mol of the polycarboxylic acid is added at temperatures above 150 C. and the temperature is rapidly raised to 200 C. as the polybasic acid reacts and water is liberated. Depending upon the number of hydroxyl groups present in the primary condensation, we may increase the molal proportions of the polybasic acid used in order that all or part of these may be reacted with the polybasic acid. The product may be cooled and used directly or at temperatures of 80 to C. the various solubilizing acid or alkylating agents may be added in quantities of .2 to .5 mol or more.

The linking by urea or other carbamyl compounds of two or more acid polyamine amide groups which are thereafter linked into long continuous resin-like chains results in products of very large molecular weight which are found to show high substantivity to the various textile fibers, such as, cotton, viscose, cellulose acetate, linen, jute, wool, nylon, and protein fibers and to give textile treatments which are permanent to washing and dry cleaning. This marked substantivity is found to arise from the presence of the urea or other similar carbarnyl groups and particularly to the very high molecular weight of the products secured by the polymeric chains formed by the polybasic acid linkages. The urea group also increases the solubility in water which is very important since such large molecules which are desirable for substantivity are poorly soluble. Water solubility is also brought about by the formation of salts at the nitrogen groups. We have found that the sensitiveness to oxidation and to heat or light of the acid polyamine amide condensations and other proposed nitrogen containing textile assistants which results in yellowing either in processing, drying, storage, or use of the treated fabrics is mainly caused by the presence of primary amino or NH: groups in the compounds and to a much lesser extent by secondary amino --(NH groups. It is the primary amino group left in the acid polyamine amide condensations which is reacted upon by the urea or other carbamyl compound and removed during the formation of our new reaction products, and we are thus able to secure compounds free of these dlmculties. Likewise, the urea and other carbamyl compounds will react with and eliminate secondary amino groups and the yellowing arising from such groups and it is an alternative under this invention to use sufilcient urea or other carbamyl compound to' combine with all the primary and secondary amino groups in the acid polyamine amide, as well as merely the single groups as shown in the general formula already given. The resistance to scorching under heat is also found to be lowered to some degree by the use of unsaturated acids as the source of R1 and while we may use them in many types of application, for products of maximum resistance we prefer the use of the saturated fatty acids.

Inasmuch as urea, thiourea, and guanidine are each decomposed readily at temperatures below 180 6. or the reaction temperatures employed, it was impossible to foresee that the large molecule substituted urea condensations would be stable at these temperatures or could be formed. Thus, the heating of urea and fatty acids at 160 does not lead to substituted ureas, but decompositions occur yielding only fatty amides as shown in U. 8. 1,989,968 and U. S. 2,109,941. In a similar way we have been unable to react urea with simple fatty amides or fatty ethanol amides and we find that it is only when we use the amide of an acid and a polyamine containing either or both a primary or secondary amino group that reaction to our substituted ureas can be secured. The condensations go readily and are free of side reactions, thus, leading to full yields of products which do not need to be purified.

In view of the fact that polyamino acid amides change rapidly at elevated temperatures and that urea compounds are relatively unstable, it could not be foreseen that the polyamino acid amide substituted carbamyl compounds could be heated to the high temperature necessary for reaction or that in view of their large molecular size they would react further with polybasic acids. However, we have found that these reactions can be carried out smoothly with theoretical yields giving products which need no further purification.

The production of resinous like materials indicates the formation of long polymeric chains and the materials become permanently fixed to the textile fibers by their substantivity on the same, thus not requiring any special curing or baking beyond the normal drying to develop I .stiifening and other effects. Where the side chains contain large fatty groups, various degrees of soft feel are permanently secured along with the stiffness or bodying clients.

The invention will be further illustrated, but is the quantities are stated in parts by weight:

Example 1 60 parts (1 mol) of acetic acid and 104 parts (1 mol) of hydroxyethyl ethylene diamine were slowly heated until one mol of water was removed. The product was an amber liquid to which 30 parts of urea (V, mol) was slowly added at 180-185 C. and the temperature raised to 190 during which time ammonia was evolved. iAt 190 C. '74 parts (1 mol equivalent) of phthalic anhydride was added and the temperature raised to 200 C. The product was an amber liquid soluble in water after treating with acetic acid, was not heat sensitive, and had the following unit formula:

H: He

Example 2 282 parts (1 mol) of oleic acid and 104 parts (1 mol) of hydroxy ethyl ethylene diamine were slowly heated until one mol of water was eliminated. 30 arts mol) of urea was then added at 1B0-18 C. and the temperature raised to 190 C. during which time ammonia was evolved.

At 190 C. 74 parts of phthalio anhydride (1 mol equivalent) were added and the temperature raised to 200 C. The product was soluble in water after treating with acetic acid and imparted a ilrm body to cloth. It had the followinc unit formula for its acetate salt:

which due to equimolar quantities of polybasic acids used have one hydroxyl and one carboxyl and group between which lie one of more repeating units as set forth in the aforementioned general formula. By reason of the'resinous nature of the products, many of these when applied to cloth show definite stiffening effects and the eifects become permanently attached to the variour textile fibers. As we have already indicated. despite the large molecular weightof thesecompounds, the solubilising groups present permit us to apply these in aqueous solutions or dispersions Example 3 7 5 mil ethanolethyl stearylamide urea was pre-' is not limited by the following examples in which pared by condensing equimolal proportions of stearic acid and hydroxyethyl ethylene diamine at 130-170 until one mol oi! water was split oi! followed by cross condensation with urea which was slowly added at ISO-185 C. (and the temperatureraised to 190 C.) To 766 parts (1 mol) of this material 98 parts (1 mol) of maleic anhydrid were added at 190 C. and the temperature raised to 200 C. during which time water was removed. The product was a dark waxy com- Example To 766 parts (1 mol) of N,N' ethanol ethylstearyl amide urea prepared as in Example 3, were added 202 parts (1 mol) of sebacic acid at 180 C. and the temperature was raised to 200 C. during which time water was distilled oil. The product was soluble in water after treatment with acetic or lactic acid. light in color. and was slightly tacky in nature. It had the following unit formula:

pound soluble in water after treatment with acid and had the following unit formula:

I I 02111 CuHzl Applied to cloth from a 2 pound in 50 gallon solution this gave a permanent finish which was slim- OH: H:

HI Hr NE NH Example 4 lar to the handle of cloth treated with ten to fifteen times as much sulphonated tallow.

Example 6 568 parts (2 mols) of stearic acid were heated with 133 parts of N-3 amino-2 propanol ethylene diamine until 1 mol of water was collected after which parts mol) of urea was slowly added at 180-185 C. and the temperature raised to 190 C. during which time ammonia was evolved. At 190 C. 101 parts (1 mol equivalent) of sebacic acid were slowly added and the temperature raised to 200 C. while water was distilled off.

little tendency to scorch on cloth. After allwlat- The product had the following unit formula:

ing with benzyl chloride to secure solubility in water, it had the following formula:

H: H: H:

NH H1 OH: NH C=O 1 13 NH =0 "Ha J3=0 =0 (BuHu (Infill I uHu Example 7 284 parts (1 mol) stearic acid were heated with 7 118 parts (1 mol) hexamethylene diamine until 1 mol of water was driven 011'. At -100 C. propylene oxide was bubbled through the condensate until 1 mol (58 parts) had been absorbed. The temperature was raised to 180 C., 30 parts (V mol) urea was slowly added and the temilerature Gradually raised to 190' 0., during which time ammonia was evolved. At 190 C. 101 parts (1 mol equivalent) sebacic acid were added slowly and the temperature raised to 200 C. The product was soluble in water after treatment with acids and had the following unit formula:

bubbled through the condensate at 80 (3. until 1 mol (44 parts) "had been absorbed. Aiter raising the temperature to 180 (2., 30 parts (/6 mol) urea was slowly added and the temperature gradually increased to 190 C. during which time ammonia was evolved. To 1 mol of the above con- Hi HI Ha H:

H: Hg

He lHs HI 3H:

tn i ln "His i'lHal Example 8 284 parts (1 mol) stenric' acid was heated with 60 parts (1' mol) ethylene diarnine until i'mol of water was driven off. At 60-80 C. ethylene oxide was bubbled through the condensate until 1 mol (44 parts) had been absorbed. The

densate, 215 parts (1 mol) of "Petreiv acid, which is defined by its producer, Hercules Powder 00., as 3 isopropyl-B-methyl 3,6-endoethyleneA tetrahydro phthalic anhydride, was added and the temperature raised to 200 C.,,during which time water was drawn 011. The product temperature raised t 180 0,, 30 parts was solublein water after treating with acetic mol) urea was slowly added and the temperature or lactic acid. It had the following unit formula:

0 O O ../--O-OHr-0Hr-N-- N-CHgCHg0-g 5- p OH:

He Ha Ha B0 on OHs Ha He He He,

H! Ks He Us a. on. V

i: 6 0 i-o time He:

Example 10 gradually raised a 190. (2., during which as.

vammonia was evolved. At 190' C.' '74 parts phthalic anhydride "(1 mol equivalent) was added and the temperature raised to 200 C. The product was soluble in water after treatment with acid and had the following unit formula:

Hi I'm JI=O =0 611ml "Eu Example 9 282 parts (I'mol) oi oleic acid was heated with 131 parts (1 mol) oi dipropyienetri'amine until one mol of water was evolved. 60 parts (1 mol) of urea was added at C. and the temperature raised to C. durinl which time ammonia was liberated. 816 parts (1 mol) of the con- E g g densate obtained above having the formula --I----O(.)Hr-CHr--N---- -NCH|CHr-O- l-- O cflna- -rm-om-onrcnr-m-onr-om-om-nn O -0 mo CnHr-ENH-OHr-OHr-Oflr- -OHs-CHs-0Hr-I$H was treated with propylene oxide at temperatures between 60-100 0. until 2 mole of oxide was absorbed. This addition product was then heated to 190' C. at which point no parts (1 mol) 0! hexanedioic acid (adipic acid) was slowly added and the temperature raised to 200' C. during which time water was split out. The product was water soluble after treatment with acids, and consisted of repeating units of the following formula:

sessed a leathery feel which was resistant to washing and dry cleaning processes.

was treated with ammonia after which the addition product with ethylene oxide was formed by bubbling ethylene oxide through the liquid amide at temperatures between 60-80 C. Its addition product had the following formula:

O C uHu--NH- CH: CH OE-GHs-NH- CHr-GHINH- GHiOHrO E 938 parts (2 mols) of this ethylene oxide addition product was condensed with 60 parts (1 mol) of urea at temperatures between mil-190 C. during which time ammonia was evolved. At 190 C. 215 parts (1 mol) of "Petrex acid, a polybasic acid defined by Hercules Powder Co. its

- producer as 3-lsopropyl-6-methyl 3,6-endoethyleneA tetra hydro phthaiic anhydride, was added and the temperature raised to 200 C. during which time water was driven off. The product was a tacky, resinous material, melting between 65-70 C. and was water soluble when treated with equimolar quantities of acids or alkylat- As many apparently widely diiferent embodiments of this invention may be made without departing from the spirit and scope thereof. it is understood that we do notllmit ourselves to the specific embodiments thereof except as defined in the appended claims.

We claim: I g 1. A condensation product having one nydroxyi and one carboxyl end group and consisting of repeating units of the following. general formula:

wherein R: is a hydrocarbon residue resulting from a polycarboxylic acid and in which R: and R4 represents simple alkylene groups of from 2 to 3 carbons and in which there is attached to the o nitrogens N1 and N2 acid amide side chains of the following general formula:

45 in which R1 represents a hydrocarbon radical resulting from an organic acid and in which the integers ,f varies from 2 to 6 and e from 0 to 3 and m from 2 to 3.

2. The salt of an acid with a condensation 50 compound described by the general formula in claim 1.

3. The alkylated product of the condensate described in claim 1 obtained by alkylating with a compound selected from the group consisting 1R1! agents. Its formula after alkylating with 55 of ethyl chloride, ethylene oxide, benzyl chloride.

dimethyl sulphate'was as follows:

H: OH;

H: HI

NE H

HOH HOH "Has 011m;

Cotton cloth impregnated with a solution containing 5 pounds per 50 gallons of water posdiethyl sulfate and dimethyl sulfate.

new,

4. The condensation products having one hydroxyi and one carboxyl end group and consisting of repeating unite oi the folio general formula: v

' wherein e variee irom to '8, f from-2 to 6. and

m from 2 to 8 are condensed at temperatures be- H: Ha 43H: (EH I I'm on IBM mam wherein n ranlea item 1 to 17 and R1 is the hydrocarbon residue from a dicarboxylic acid.

5. A new chemical compound having one hydroxyl and one carboxyl one group and consistin: of repeating unite oi the iollowin: formula:

6. A new chemical compound having one hydroxyl and one carbonyl end group and consisting oi repeating units oi the following formula:

of repeating units of the 10110 E 43 0 one 8. A process or iorming a oondonsation product as dennea in claim 1 in which equimolar quantities 0! an orlanic monoeai'boallic acid and an alkylol polyemine oi the following general formula wherein e varies from 0 to 8, r from 2 to 0, and m irom 2 to 3 are condenser! at temperatures between 180-170 C. and thereai'ter reacted with e5 one-halt mol oi urea at 170-200 C. and thereaiter reacted with equimolar quantities of a polycarboxylic acid at tomperoturee irom -200 C.

0. A process oi iormina a condemation product l8 defined in claim 1 in which iquantities'oi an oraanic monocarhoaylio coin! and an aglol .pelyamine oi the to normal form Nile-t (can nr-Nfilr-(CBI)! tween -170" C. and thereaiter reacted with one-halt moi of urea at -200 C. and-thereafter further reacted with luflioient polycarbowlio acid to react with "all of the hydroayl groups present.

10. A process or forming a condensation prodnot as defined in claim 1 in which equimolar quantities of an organic monooarboxyllo acid and an allmol polyamine of the following lensral formula ee whereinevarieairomilto8,i2te0,m

from 2 to 8 are condensed at turee bebetween -170 C. and thereafter react with one-hair moi oi urea at temperatures between 170-200 0. and thereafter further reacted with an equimolar cuentity ci a polrearbosylio acid at temperatures irom 100-200 C. and thereafter solubilieed by adding one moi of acid.

11. A procm of running a condensation product as (led in claim 1 in which equimolar quantiti or monoc r i acid-and an lyomino oi the My metal formula [(CHQM- --tm-(CEel--0H wherein e variee from 0 to 8, I iron 2 to 0, and in from 2 to 8 are condensed at temperaturee he-' tween 120-170 C. and thereafter reacted with one-hair mol oi urea at 170-200 0. and there- --II(GBah-O8 7 alter-reacted with an will? 0112110197 Bl polycarboxylic acid at 150-200 C. and solubilized by the addition of onemol of a water soluble acid.

12. A process of forming a condensation product as defined in claim 1 in which equimolar quantities of an oraanic monocarboxylic acid and an alkylol polyamine of the followin: zener'al formula wherein e varies from to 3, 1 from 2 to 8, and m from 2 to 3 are condensed at temperatures between 130-170" 6., said condensate containing free secondary amino aroupe which is then reacted with one-half mol of urea for each secondary amino group at temperatures between 170-200 C. and thereafter further reacted with an equimolar quantity of a polycarboxyiic acid at temperatures between USO-200 C.

13. A process of forming a condensation product as deilned in claim 1 in which equimolar quantities oi an organic monocarboxylic acid and an alkylol poiyamine oi the following general formula wherein e varies from 0 to 3. I from 2 to 8, and m from 2 to 3 are condensed at temperatures between -170 C. and thereafter reacted with one-half mol of urea at 170-200 C. and thereafter reacted with an equimolar quantity oi polycarboxylic acid at -200 C. and soiubilized by reacting with one mol of an alnlatin alent selected from the group consisting of ethyl chloride ethylene oxide, bensyl chloride, dimethyl sulfate and diethyl sulfate.

14. A textile material impregnated with a condensation product as described in claim 1.

15. A textile material impremated with an alkylated condensation product obtained by alkylating a condensation product as described in claim 1 with a compound selected from the group consisting of ethyl chloride, ethylene oxide, benzyl chloride, diethyl sulfate and dlmethyl sulfate.

16. A textile material impregnated with the salt which is the addition product oi an acid to a condensation product as described in claim 1.

WIILARD L. MORGAN. EARLE D. MOLIOD. 

